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Patent 2827472 Summary

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(12) Patent: (11) CA 2827472
(54) English Title: LUBRICATING COMPOSITION AND METHOD OF LUBRICATING DRIVELINE DEVICE
(54) French Title: COMPOSITION LUBRIFIANTE ET PROCEDE DE LUBRIFICATION D'UN DISPOSITIF DE TRANSMISSION
Status: Granted
Bibliographic Data
(51) International Patent Classification (IPC):
  • C10M 163/00 (2006.01)
(72) Inventors :
  • BARTON, WILLIAM R. S. (United Kingdom)
(73) Owners :
  • THE LUBRIZOL CORPORATION (United States of America)
(71) Applicants :
  • THE LUBRIZOL CORPORATION (United States of America)
(74) Agent: SMART & BIGGAR LP
(74) Associate agent:
(45) Issued: 2019-08-20
(86) PCT Filing Date: 2012-02-15
(87) Open to Public Inspection: 2012-08-23
Examination requested: 2017-02-15
Availability of licence: N/A
(25) Language of filing: English

Patent Cooperation Treaty (PCT): Yes
(86) PCT Filing Number: PCT/US2012/025159
(87) International Publication Number: WO2012/112635
(85) National Entry: 2013-08-15

(30) Application Priority Data:
Application No. Country/Territory Date
61/443, 329 United States of America 2011-02-16

Abstracts

English Abstract

The present invention relates to a lubricating composition containing: an oil of lubricating viscosity, a non-borated dispersant, a detergent, and an antiwear package comprising (a) a derivative of a hydroxycarboxylic acid, (b) an amine salt of a phosphoric acid ester, and (c) a phosphite having at least one hydrocarbyl group with 4 or more carbon atoms. The invention further provides for a method of lubricating a driveline device application by employing a lubricating composition containing the antiwear package.


French Abstract

La présente invention a pour objet une composition lubrifiante contenant : une huile de viscosité lubrifiante, un dispersant non boré, un détergent, et un ensemble anti-usure comprenant (a) un dérivé d'un acide hydroxycarboxylique, (b) un sel d'amine d'un ester d'acide phosphorique, et (c) un phosphite ayant au moins un groupe hydrocarbyle ayant 4 atomes de carbone ou plus. La présente invention concerne en outre un procédé de lubrification d'une application de dispositif de transmission par l'utilisation d'une composition lubrifiante contenant l'ensemble anti-usure.
Claims

Note: Claims are shown in the official language in which they were submitted.


CLAIMS
What is claimed is:
1. A method of lubricating a driveline device comprising supplying a
lubricating
composition to the driveline device, wherein the driveline device contains a
synchronizer
or axle, and wherein the lubricating composition comprises:
an oil of lubricating viscosity,
0.01 wt % to 2 wt % of a non-borated dispersant,
0.1 wt % to 1 wt % of a detergent, and
an antiwear package comprising
(a) 0.05 wt % to 1.5 wt % of a derivative of a hydroxycarboxylic acid,
(b) 0.1 wt % to 2.5 wt % of an amine salt of a phosphoric acid ester, and
(c) 0.05 wt % to 2.0 wt % of a phosphite having at least one hydrocarbyl group

with 4 or more carbon atoms.
2. The method of claim 1, wherein the synchronizer operating surface
comprises
brass, carbon, molybdenum, phenolic resin, or a sintered metal or mixtures
thereof.
3. The method of claim 1 or 2, wherein the lubricating composition
comprises:
an oil of lubricating viscosity,
0.4 wt % to 1.2 wt % of a non-borated dispersant,
0.4 wt % to 1.0 wt % of a detergent, and
an antiwear package comprising
(a) 0.05 wt % to 0.8 wt % of a derivative of a hydroxycarboxylic acid,
(b) 0.1 wt % to 1 wt % of an amine salt of a phosphoric acid ester, and
(c) 0.1 wt % to 1.0 wt % of a phosphite having at least one hydrocarbyl group
with
4 or more carbon atoms.
32


4. The method of any one of claims 1 to 3, wherein the detergent is a
sulphonate, a
phenate, or mixtures thereof.
5. The method of claim 4, wherein the phenate is an alkyl phenate, an
aldehyde-
coupled alkyl phenate, a sulphurised alkyl phenate, or mixtures thereof.
6. The method of any one of claims 1 to 5, wherein the non-borated
dispersant is a
succinimide dispersant, or mixtures thereof.
7. The method of any one of claims 1 to 6, wherein the non-borated
dispersant is a
polyisobutylene succinimide, wherein the polyisobutylene from which the
polyisobutylene
succinimide is derived has a number average molecular weight in the range of
350 to 5000,
or 500 to 3000, or 750 to 2200, or 750 to 1150.
8. The method of any one of claims 1 to 7, wherein the non-borated
dispersant is a
non-borated succinimide, and wherein the non-borated dispersant is in a
mixture with a
borated dispersant.
9. The method of any one of claims 1 to 8, wherein the non-borated
dispersant is a
polyisobutylene succinimide derived from an aliphatic polyamine selected from
the group
consisting of ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylene-
pentamine, pentaethylenehexamine, polyamine still bottoms, and mixtures
thereof.
10. The method of any one of claims 1 to 9, wherein the non-borated
dispersant is a
polyisobutylene succinimide derived from an aliphatic polyamine selected from
the group
consisting of tetraethylenepentamine, pentaethylenehexamine, polyamine still
bottoms,
and mixtures thereof.
11. The method of any one of claims 1 to 10, wherein the derivative of a
hydroxycarboxylic acid is represented by the formula:

33


Image
wherein
n and m are independently integers of 1 to 5;
X is an aliphatic or alicyclic group, or an aliphatic or alicyclic group
containing an oxygen
atom in the carbon chain, or a substituted group of the foregoing types, said
group
containing up to 6 carbon atoms and having n+m available points of attachment;

each Y is independently -O-, or >NR1 or two Ys together representing the
nitrogen of an
imide structure R-N< formed between two carbonyl groups; and
each R and R1 are independently hydrogen or a hydrocarbyl group, provided that
at least
one R or R1 group is a hydrocarbyl group; each R2 is independently hydrogen, a

hydrocarbyl group or an acyl group, further provided that at least one -OR2
group is located
on a carbon atom within X that is a or p to at least one of the -C(O)-Y-R
groups.
12. The method of any one of claims 1 to 11, wherein the derivative of a
hydroxycarboxylic acid is a derivative of tartaric acid or a derivative of
citric acid.
13. The method of any one of claims 1 to 12, wherein the amine salt of a
phosphoric
acid ester is represented by the formula:
Image
wherein
R3 and R4 are independently hydrogen or a hydrocarbyl group (such as a
hydrocarbon
group) typically containing 4 to 40, or 6 to 30, or 6 to 18, or 8 to 18 carbon
atoms, with the
proviso that at least one is a hydrocarbon group; and

34


R5, R6, R7 and R8 are independently hydrogen or a hydrocarbyl group, with the
proviso that
at least one is a hydrocarbyl group.
14. The method
of any one of claims 1 to 13, wherein the phosphite is represented by
the formulae:
Image
wherein at least two of R9, R10 and R11 is a hydrocarbyl group containing at
least 4 carbon
atoms and the other is hydrogen or a hydrocarbyl group.


Description

Note: Descriptions are shown in the official language in which they were submitted.


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TITLE
Lubricating Composition and Method of Lubricating Driveline Device
FIELD OF INVENTION
[0001] The present invention relates to a lubricating composition
containing:
an oil of lubricating viscosity, a non-borated dispersant, a detergent, and an

antiwear package comprising (a) a derivative of a hydroxycarboxylic acid, (b)
an
amine salt of a phosphoric acid ester, and (c) a phosphite having at least one

hydrocarbyl group with 4 or more carbon atoms. The invention further provides
for a method of lubricating a driveline device application by employing a
lubricating composition containing the antiwear package.
BACKGROUND OF THE INVENTION
[0002] Oxidation of an oil of lubricating viscosity, especially an
organic
petroleum fluid, occurs in the presence of oxygen which leads to increased
viscosity and sludge and/or deposit formation. Sludge and/or deposit formation

is produced by a number of different mechanisms such as degradation of oil
and decomposition products of lubricant additives. Using known lubricant
additives containing an amine salt of a phosphorus compound such as many
antiwear agents and friction modifiers is believed to contribute to the
formation
of sludge and/or deposit formation. The presence of sludge and other deposits
interferes with seal performance leading to leakage and ultimately equipment
failure for gears or bearings. However, many amine salts of phosphorus
compounds also perform antiwear or extreme pressure functions.
[0003] One of the important parameters influencing durability or wear
resistance of devices employing a lubricating composition is the effectiveness

of phosphorus antiwear or extreme pressure additives at providing devices with

appropriate protection under various conditions of load and speed. However,
many of the phosphorus antiwear or extreme pressure additives contain sulphur.

Due to increasing environmental concerns, the presence of sulphur in antiwear
or extreme pressure additives is becoming less desirable. In addition, many of

the sulphur-containing antiwear or extreme pressure additives evolve volatile
sulphur species, resulting in lubricating compositions containing antiwear or
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extreme pressure additives having an odour, which may also be detrimental to
the environment or evolve emissions that may be higher than increasingly
tighter health and safety legislation specifies.
[0004] A lubricating composition having the correct balance of phosphorus
antiwear or extreme pressure additives provides driveline power transmitting
devices with prolonged life and efficiency with controlled deposit formation
and oxidation stability. However, many of the antiwear or extreme pressure
additives employed have at least one of (i) limited extreme pressure and
antiwear performance over a wide range of operating conditions, (ii) limited
oxidative stability, (iii) tendency to form deposits, or (iv) tendency to
cause
corrosion (for example copper corrosion). In addition, many phosphorus
antiwear or extreme pressure additives typically contain sulphur, which
results
in an odorous lubricating composition containing the phosphorus antiwear or
extreme pressure additives. A number of references disclosing antiwear
chemistry are discussed below.
[0005] In addition, driveline devices often require certain frictional
properties from a lubricant to provide the ability of the device to operate,
e.g., a
manual transmission to perform gear changes. For the gear change to be
successful, the transmission must match the speeds of the input and output
shafts. Matching of speeds may be accomplished by a synchronizer by which
the synchronizing parts (plate to plate or ring to cone) are reduced to
relative
zero velocity. If these parts do not obtain zero relative velocity, then a
phenomenon known as synchronizer clashing (sometimes referred to as
crashing) occurs. Clashing of the synchronizer results when the dynamic
coefficient of friction building between the engaging synchronizer parts
(plate
to plate or ring to cone) falls below a critical minimum value.
[0006] A number of publications generally disclose lubricants containing
hydroxy carboxylic acid derivatives or carboxylic acid derivatives, typically
for
use an antiwear agent. The publications include International publications WO
2006/044411, WO 2005/087904, WO 2008/070307, and U.S. Patents
4,326,972; 4,952,328; 5,338,470; and 4,237,022.
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[0007] International publication W02010/141003 discloses a driveline
device lubricated with a composition containing a derivative of a
hydroxycarboxylic acid and a phosphorus compound that may be either (i) a
hydroxy-substituted di- ester of (thio)phosphoric acid, or (ii) a
phosphorylated
hydroxy-substituted di- or tri- ester of (thio)phosphoric acid.
[0008] International patent application PCT/US2010/045145 (based on US
Patent application serial number 61/234722, filed 18 August 2009) discloses a
method for lubricating a driveline device comprising supplying to the
driveline
device a lubricating composition comprising an oil of lubricating viscosity
and an
antiwear package wherein the antiwear package comprises (a) a derivative of a
hydroxycarboxylic acid, and (b) a phosphorus compound selected from the
group consisting of an amine salt of a phosphate hydrocarbon ester, a
phosphite
having at least one hydrocarbyl group with 4 or more carbon atoms, and
mixtures thereof.
SUMMARY OF THE INVENTION
[0009] The inventors of this invention have discovered that a lubricating
composition and method as disclosed herein is capable of providing acceptable
levels of at least one of (i) wear, (ii) scuffing, (iii) fatigue, (iv)
ridging, (v)
extreme pressure performance, (vi) fuel economy/efficiency (typically
improving fuel economy/efficiency), (vii) oxidation control (typically
reducing
or preventing oxidation), (viii) friction performance and (ix) deposit
control.
Improved wear or fatigue performance in a driveline device, including
transmission or differential gears and/or bearings, is desirable.
[0010] In one embodiment the invention provides a lubricating composition
comprising: an oil of lubricating viscosity, a non-borated dispersant, a
detergent, and an antiwear package comprising (a) a derivative of a
hydroxycarboxylic acid, (b) an amine salt of a phosphoric acid ester, and (c)
a
phosphite having at least one hydrocarbyl group with 4 or more carbon atoms.
[0011] In one embodiment the phosphorus compound may be an amine salt
of a phosphoric acid hydrocarbon ester or mixtures thereof.
[0012] In one embodiment the derivatives of hydroxycarboxylic acid
include imides, di-esters, di-amides, ester-amides derivatives of either
tartaric
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acid or citric acid. Typically the derivatives of hydroxycarboxylic acid are
imides, di-esters, di-amides, ester-amides derivatives of tartaric acid.
[0013] In one embodiment the invention provides a method of lubricating a
mechanical device with a lubricating composition disclosed herein. The
mechanical device may be a driveline device. The driveline device may be a
manual transmission that may or may not contain a synchronizer system, or an
axle. In one embodiment the driveline device contains a synchronizer, or axle.

In one embodiment the driveline device contains a synchronizer.
[0014] The synchronizer system may have an operating surface comprising
brass, carbon, molybdenum, phenolic resin, or a sintered metal (typically
bronze), or mixtures thereof.
[0015] In different embodiments the lubricating compositions disclosed
herein contain 0 ppm to 500 ppm, or 5 ppm to 300 ppm, or 20 ppm to 250 ppm
of molybdenum.
[0016] In different embodiments the lubricating compositions disclosed
herein may have a sulphur content of greater than 0.3 wt %, or 0.4 wt % to 5
wt
%, or 0.5 wt % to 3 wt %, 0.8 wt % to 2.5 wt %, or 1 wt % to 2 wt % of the
lubricating composition.
[0017] In one embodiment the invention provides for the use of a
lubricating
composition as disclosed herein for providing acceptable levels of at least
one
of (i) wear, (ii) scuffing, (iii) fatigue, (iv) ridging, (v) extreme pressure
performance, (vi) fuel economy/efficiency (typically improving fuel
economy/efficiency), (vii) oxidation control (typically reducing or preventing

oxidation), (viii) friction performance and (ix) deposit control.
DETAILED DESCRIPTION OF THE INVENTION
[0018] The present invention provides a lubricating composition and a
method for lubricating a driveline device as disclosed above.
Detergent
[0019] The detergent may be an overbased detergent, a non-overbased
detergent, or mixtures thereof.
[0020] The preparation of a detergent is known in the art. Patents
describing the preparation of overbased detergents include U.S. patents
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2,501,731; 2,616,905; 2,616,911; 2,616,925; 2,777,874; 3,256,186; 3,384,585;
3,365,396; 3,320,162; 3,318,809; 3,488,284; and 3,629,109.
[0021] As used herein the TBN values quoted and associated range of TBN
is on
"an as is basis," i.e., containing conventional amounts of diluent oil which
is used to
handle viscosity. Conventional amounts of diluent oil typically range from 30
wt %
to 60 wt % (often 40 wt % to 55 wt %) of the detergent component.
[0022] The detergent may be a non-overbased detergent (may also be
referred to as a neutral detergent). The TBN of a non-overbased detergent may
be 20 to less than 200, or 30 to 100, or 35 to 50 mg KOH/g. The TBN of a non-
overbased detergent may also be 20 to 175, or 30 to 100 mg KOH/g. When a
non-overbased detergent is prepared from a strong acid such as a hydrocarbyl-
substituted sulphonic acid, the TBN may be lower (for example 0 to 50 mg
KOH/g, or 10 to 20 mg KOH/g).
[0023] The detergent may be an overbased detergent, which may have a TBN
of greater than 200 mg KOH/g (typically 250 to 600, or 300 to 500 mg KOH/g).
[0024] A more detailed description of the expressions "metal ratio", TBN
and "soap content" are known to a person skilled in the art and explained in
standard textbook entitled "Chemistry and Technology of Lubricants", Third
Edition, Edited by R. M. Mortier and S. T. Orszulik, Copyright 2010, pages 219

to 220 under the sub-heading 7.2.5. Detergent Classification.
[0025] The detergent may be formed by the reaction of a basic metal
compound and an acidic detergent substrate. The acidic detergent substrate may

include an alkyl phenol, an aldehyde-coupled alkyl phenol, a sulphurised alkyl

phenol, an alkyl aromatic sulphonic acid (such as, alkyl naphthalene sulphonic

acid, alkyl toluene sulphonic acid or alkyl benzene sulphonic acid), an
aliphatic
carboxylic acid, a calixarene, a salixarene, an alkyl salicylic acid, or
mixtures
thereof.
[0026] The metal basic compound is used to supply basicity to the
detergent. The basic metal compound is a compound of a hydroxide or oxide of
the metal. Within the metal compound, the metal is typically in the form of an

ion. The metal may be monovalent, divalent, or trivalent. When monovalent,
the metal ion M may be an alkali metal, when divalent, the metal ion M may be

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an alkaline earth metal, and when trivalent the metal ion M may be aluminium.
The alkali metal may include lithium, sodium, or potassium, or mixtures
thereof, typically sodium. The alkaline earth metal may include magnesium,
calcium, barium or mixtures thereof, typically calcium or magnesium.
[0027] Examples of metal basic compounds with hydroxide functionality
include lithium hydroxide, potassium hydroxide, sodium hydroxide, magnesium
hydroxide, calcium hydroxide, barium hydroxide and aluminium hydroxide.
Suitable examples of metal basic compounds with oxide functionality include
lithium oxide, magnesium oxide, calcium oxide and barium oxide. The oxides
and/or hydroxides can be used alone or in combination. The oxides or
hydroxides may be hydrated or dehydrated, although hydrated is typical. In
one embodiment the metal basic compound may be calcium hydroxide, which
may be used alone or mixtures thereof with other metal basic compounds.
Calcium hydroxide is often referred to as lime. In one embodiment the metal
basic compound may be calcium oxide which can be used alone or mixtures
thereof with other metal basic compounds.
[0028] Collectively, when the alkyl phenol, the aldehyde-coupled alkyl
phenol,
and the sulphurised alkyl phenol are used to prepare a detergent, the
detergent may
be referred to as a phenate. The phenate may be an alkyl phenate, an aldehyde-
coupled alkyl phenate, a sulphurised alkyl phenate, or mixtures thereof.
[0029] The TBN of a phenate may vary from less 200, or 30 to 175
typically 150
to 175) mg KOH/g for a neutral phenate to 200 or more to 500, or 210 to 400
(typically 230 to 270) mg KOH/g for an overbased phenate.
[0030] The alkyl group of a phenate (i.e., an alkyl phenate) may contain
4 to 80,
or 6 to 45, or 8 to 20, or 9 to 15 carbon atoms.
[0031] In one embodiment the detergent may be a sulphonate, or mixtures
thereof The sulphonate may be prepared from a mono- or di- hydrocarbyl-
substituted benzene (or naphthalene, indenyl, indanyl, or bicyclopentadienyl)
sulphonic acid, wherein the hydrocarbyl group may contain 6 to 40, or 8 to 35
or 9 to 30 carbon atoms.
[0032] The hydrocarbyl group may be derived from polypropylene or a
linear or branched alkyl group containing at least 10 carbon atoms. Examples
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of a suitable alkyl group include branched and/or linear decyl, undecyl,
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
octadecenyl, nonodecyl, eicosyl, un-eicosyl, do-eicosyl, tri-eicosyl, tetra-
eicosyl, penta-eicosyl, hexa-eicosyl or mixtures thereof
[0033] In one embodiment the hydrocarbyl-substituted sulphonic acid may
include polyprop ene b enzenesulphonic acid and/or C16-C24 alkyl
benzenesulphonic acid, or mixtures thereof.
[0034] In one embodiment the sulphonate detergent may be a predominantly
linear alkylbenzene sulphonate detergent having a metal ratio of at least 8 as
is
described in paragraphs [0026] to [0037] of US Patent Application 2005065045
(and
granted as US 7,407,919). In some embodiments the linear alkyl group may be
attached to the benzene ring anywhere along the linear chain of the alkyl
group, but
often in the 2, 3 or 4 position of the linear chain, and in some instances
predominantly in the 2 position.
[0035] When neutral or slightly basic, a sulphonate detergent may have
TBN of less than 100, or less than 75, typically 20 to 50 mg KOH/g, or 0 to 20

mg KOH/g.
[0036] When overbased, a sulphonate detergent may have a TBN greater
than 200, or 300 to 550, or 350 to 450 mg KOH/g.
[0037] A salicylate detergent may be derived from an alkyl-substituted
salicylic acid. The TBN of a neutral salicylate may be 50 to 200, or 75 to 175

mg KOH/g. An overbased salicylate may have a TBN of greater than 150 to 400,
or 175 to 350 mg KOH/g.
[0038] The alkyl group of a salicylate may contain 4 to 80, or 6 to 45,
or 8 to
20, or 9 to 18 carbon atoms. In different embodiments the alkyl group of a
salicylate may contain 12 or 16 carbon atoms.
[0039] Chemical structures for sulphonates, phenates and salicylates
detergents are known to a person skilled in the art. The standard textbook
entitled "Chemistry and Technology of Lubricants", Third Edition, Edited by R.

M. Mortier and S. T. Orszulik, Copyright 2010, pages 220 to 223 under the sub-
heading 7.2.6 provide general disclosures of said detergents and their
structures.
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[0040] A
saligenin detergent is described in US Patent 7,285,516 in column 3,
line 47 to column 5, line 63.
[0041] A
salixarate detergent is described in US Patent 7,285,516 in column 5,
line 64 to column 7, line 53. In general terms a salixarate is derived from
coupling a hydro carbyl-substituted phenol with (an optionally hydrocarbyl-
substituted) salicylic acid in the presence of formaldehyde.
Salixarate
derivatives and methods of their preparation are also described in US Patent
6,200,936 and PCT Publication WO 01/56968. It is believed that the salixarate
derivatives have a predominantly linear, rather than macrocyclic, structure,
although both structures are intended to be encompassed by the term
"salixarate." An overbased salixarate may have a TBN of 170 to 300 mg
KOH/g. A neutral salixarate may have a TBN of 50 to less than 170 mg KOH/g.
[0042] In one
embodiment the detergent may be a carboxylate derived from
an aliphatic carboxylic acid. The aliphatic acid may contain 6 to 30, or 7 to
16
carbon atoms. Examples of a suitable carboxylic acid include caprylic acid,
capric acid, lauric acid, myristic acid, myristoleic acid, decanoic acid,
dodecanoic acid, pentadecanoic acid, palmitic acid, palmitoleic acid, margaric

acid, stearic acid, 12-hydroxystearic acid, oleic acid, ricinoleic acid,
linoleic
acid, arachidic acid, gadoleic acid, eicosadienoic acid, behenic acid, erucic
acid, tall oil fatty acids, rapeseed oil fatty acid, linseed oil fatty acid,
or
mixtures thereof. In one embodiment the aliphatic acids are oleic acid or tall

oil fatty acid.
[0043] The
carboxylate may have a metal ratio of 0.2 to 10, or from 0.5 to 7,
or from 0.7 to 5. When overbased, the metal ratio is greater than one.
[0044] In one
embodiment the acidic or neutralised detergent substrate
comprises mixtures of at least two of said substrates. When two or more
detergent substrates are used, the overbased detergent formed may be described

as a complex/hybrid. The overbased metal-containing detergent may also
include "hybrid" detergents formed with mixed surfactant systems including
phenate and/or sulphonate components, e.g. phenate/salicylates, sulphonate/
phenates, sulphonate/salicylates, sulphonates/phenates/salicylates, as
described;
for example, in US Patents 6,429,178; 6,429,179; 6,153,565; and 6,281,179.
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Where, for example, a hybrid sulphonate/phenate detergent is employed, the
hybrid detergent would be considered equivalent to amounts of distinct phenate

and sulphonate detergents introducing like amounts of phenate and sulphonate
soaps, respectively.
[0045] The detergent may be a salixarate, a salicylate, a saligenin, a
sulphonate, a phenate, or mixtures thereof. Alternatively, the detergent may
be
a salixarate, a salicylate, or mixtures thereof The detergent may be a
saligenin,
a phenate, or mixtures thereof. In one embodiment the detergent may be a
sulphonate, a phenate, or mixtures thereof
[0046] The detergent may contain an alkaline earth or alkali metal
(typically
sodium, barium, calcium, or magnesium), such as calcium or magnesium.
Typically the detergent may be zinc, barium sodium, calcium or magnesium salt
of a phenate, sulphur-containing phenate, sulphonate, salixarate or
salicylate.
[0047] The detergent may be borated or non-borated.
[0048] The detergent may be present at 0.1 wt % to 1 wt %, or 0.2 wt % to
0.9 wt % or 0.1 wt % to 0.4 wt %, or 0.4 wt % to 1.0 wt %, of the lubricating
composition.
Non-Borated Dispersant
[0049] The non-borated dispersant of the invention may be a succinimide
dispersant, a Mannich dispersant, a succinamide dispersant, a polyolefin
succinic acid ester, amide, or ester-amide, or mixtures thereof. In one
embodiment the non-borated dispersant may be a succinimide dispersant.
[0050] The non-borated dispersant may be an N-substituted long chain
alkenyl succinimide, a Mannich base, or mixtures thereof. Examples of N-
substituted long chain alkenyl succinimide include polyisobutylene succin-
imide, wherein the polyisobutylene from which the polyisobutylene succinic
anhydride is derived has a number average molecular weight in the range of
350 to 5000, or 500 to 3000, or 750 to 2200, or 750 to 1150.
[0051] The non-borated dispersant may be a non-borated succinimide, and
the non-borated dispersant may be in a mixture with a borated dispersant
(typically a borated polyisobutylene succinimide).
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[0052] The non-borated dispersant may be formed by reaction of a
substituted acylating agent with a polyamine (typically having two or more
reactive sites). For example, the substituted acylating agent may be a
polyisobutylene succinic anhydride and the polyamine.
[0053] The polyamine may be an alkylenepolyamine. The alkylene-
polyamine may include an ethylenepolyamine, a propylenepolyamine, a
butylenepolyamine, or mixtures thereof. Examples of propylenepolyamine
include propylenediamine, dipropylenetriamine and mixtures thereof.
[0054] In one embodiment the polyamine is selected from the group
consisting of ethylenediamine, diethylenetriamine, triethylenetetramine,
tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms and
mixtures thereof.
[0055] The non-borated dispersant may be a polyisobutylene succinimide
derived from an aliphatic polyamine selected from the group consisting of
ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepent-
amine, pentaethylenehexamine, polyamine still bottoms, and mixtures thereof.
[0056] The non-borated dispersant may be a polyisobutylene succinimide
derived from an aliphatic polyamine selected from the group consisting of
tetraethylenepentamine, pentaethylenehexamine, polyamine still bottoms, and
mixtures thereof.
[0057] The polyamine may also be an a,13-diaminoalkane. Examples of the
a,I3-diaminoalkane include diaminopropane, diaminobutane or mixtures
thereof Specific diaminoalkanes are selected from the group consisting of N-
(2-aminoethyl)- 1,3 -propane diamine, 3,3 '-diamine-N-methyldipropylamine,
tris(2-aminoethyl)amine, N,N-bis(3 -aminopropy1)- 1,3 -propane diamine, N,N'-
1,2-ethanediylbis-(1,3-propane diamine) and mixtures thereof.
[0058] In one embodiment the polyamine may include di-(trimethylene)-
triamine, piperazine, diaminocyclohexanes, or mixtures thereof.
[0059] The non-borated dispersant may be prepared/obtained/obtainable
from reaction of succinic anhydride by an "ene" or "thermal" reaction, by what

is referred to as a "direct alkylation process." The "ene" reaction mechanism
and general reaction conditions are summarised in "Maleic Anhydride", pages,

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147-149, Edited by B.C. Trivedi and B.C. Culbertson and Published by Plenum
Press in 1982. The non-borated dispersant prepared by a process that includes
an "ene" reaction may be a polyisobutylene succinimide having a carbocyclic
ring present on less than 50 mole %, or 0 to less than 30 mole %, or 0 to less

than 20 mole %, or 0 mole % of the non-borated dispersant molecules. The
"ene" reaction may have a reaction temperature of 180 C to less than 300 C,
or 200 C to 250 C, or 200 C to 220 C.
[0060] The non-borated dispersant may also be obtained/obtainable from a
chlorine-assisted process, often involving Diels-Alder chemistry, leading to
formation of carbocyclic linkages. The process is known to a person skilled in

the art. The chlorine-assisted process may produce a non-borated dispersant
that is a polyisobutylene succinimide having a carbocyclic ring present on 50
mole % or more, or 60 to 100 mole % of the non-borated dispersant molecules.
Both the thermal and chlorine-assisted processes are described in greater
detail
in U.S. Patent 7,615,521, columns 4-5 and preparative examples A and B.
[0061] The non-borated dispersant may have a carbonyl to nitrogen ratio
(CO:N ratio) of 5:1 to 1:10, 2:1 to 1:10, or 1:1 to 1:10, or 1:1 to 1:5, or
1:1 to
1:2. In one embodiment the non-borated dispersant may have a CO:N ratio of
1:1 to 1:10, or 1:1 to 1:5, or 1:1 to 1:2.
[0062] In one embodiment the non-borated dispersant may be a reaction
product of a hydrocarbyl-substituted phenol, an aldehyde, and an amine or
ammonia. The hydrocarbyl substituent of the hydrocarbyl-substituted phenol
may have 10 to 400 carbon atoms, in another instance 30 to 180 carbon atoms,
and in a further instance 10 or 40 to 110 carbon atoms. This hydrocarbyl
substituent may be derived from an olefin or a polyolefin. Useful olefins
include alpha-olefins, such as 1-decene, which are commercially available.
[0063] The non-borated dispersant may be present at (on an oil free
basis)
0.01 wt % to 2 wt %, or 0.025 wt % to 1.5 wt %, or 0.025 wt % to 0.4 wt %, or
0.4 wt % to 1.2 wt % of the lubricating composition.
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Compound Derived from Hydroxy-Carboxylic Acid
[0064] The invention provides a lubricating composition containing a
compound derived from a hydroxy-carboxylic acid. The compound derived from a
hydroxy-carboxylic acid may be represented by the formula:
/ 0
µ \
X¨E0R2 )
C
\R-Yin m
wherein
n and m may be independently integers of 1 to 5;
X may be an aliphatic or alicyclic group, or an aliphatic or alicyclic group
containing an oxygen atom in the carbon chain, or a substituted group of the
foregoing types, said group containing up to 6 carbon atoms and having n+m
available points of attachment (that is, although there may be additional
valences on
X which are satisfied by, e.g., bonding to one or more hydrogen atoms, there
will be
at least sufficient available valences to attach to the n+m number of groups
for the
particular hydroxy-carboxylic acid);
each Y may be independently ¨0¨, or >NR1 or two Ys together may represent the
nitrogen of an imide structure R-N< formed between two carbonyl groups; and
each R and R1 may be independently hydrogen or a hydrocarbyl group, provided
that at least one R or R1 group is a hydrocarbyl group; each R2 may be
independently hydrogen, a hydrocarbyl group or an acyl group, further provided
that
at least one -0R2 group is located on a carbon atom within X that is a or 0 to
at least
one of the -C(0)-Y-R groups.
[0065] The compound derived from the hydroxy-carboxylic acid may be
derived from glycolic acid (n and m both equal 1), malic acid (n = 2, m = 1),
tartaric
acid (n and m both equal 2), citric acid (n = 3, m = 1), or mixtures thereof
In one
embodiment the compound derived from the hydroxy-carboxylic acid may be
derived from tartaric acid or citric acid. In one embodiment the compound
derived
from the hydroxy-carboxylic acid may be derived from tartaric acid.
[0066] The compound derived from the hydroxy-carboxylic acid may be an
amide, ester or imide derivative of a hydroxy-carboxylic acid, or mixtures
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thereof In one embodiment the compound derived from the hydroxy-carboxylic
acid may be an amide, ester or imide derivative of a hydroxy-carboxylic acid.
For example the compound derived from the hydroxy-carboxylic acid may an
ester or imide of tartaric acid, or the compound derived from the hydroxy-
carboxylic acid may an ester or imide of citric acid.
[0067] In one
embodiment the compound derived from the hydroxy-carboxylic
acid may be at least one of a hydroxy-carboxylic acid di-ester, a hydroxy-
carboxylic acid di-amide, a hydroxy-carboxylic acid di-imide, a hydroxy-
carboxylic acid mono-imide, a hydroxy-carboxylic acid ester-amide, a hydroxy-
carboxylic acid ester-imide, and a hydroxy-carboxylic acid imide-amide. In one

embodiment the amide, ester or imide derivative of a hydroxy-carboxylic acid
may derived from at least one of the group consisting of a hydroxy-carboxylic
acid di-ester, a hydroxy-carboxylic acid di-amide, a hydroxy-carboxylic acid
mono-imide, and a hydroxy-carboxylic acid ester-amide.
[0068] Each R,
R1 and R2 group of the compound derived from the hydroxy-
carboxylic acid may be a linear or branched alkyl group each having 1 to 150,
or
8 to 30, or 8 to 20 carbon atoms. The ester derivatives of the hydroxy-
carboxylic acid may be formed by the reaction of an alcohol with hydroxy-
carboxylic acid. The
alcohol includes both monohydric alcohols and
polyhydric alcohols. The carbon atoms of the alcohol may be linear chains,
branched chains, or mixtures thereof.
[0069]
Examples of a suitable branched alcohol include 2-ethylhexanol, iso-
tridecanol, iso-octyl alcohol, Guerbet alcohols, or mixtures thereof.
[0070]
Examples of a monohydric alcohol include methanol, ethanol,
propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol,
undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol,
heptadecanol, octadecanol, nonadecanol, eicosanol, or mixtures thereof In one
embodiment the monohydric alcohol contains 8 to 20 carbon atoms.
[0071] In one
embodiment the imide derivatives of a hydroxy-carboxylic
acid may be tartrimides, typically containing 8 to 20 carbon atoms. Amines
used to prepare imides may include alkyl amines (such as n-hexylamine
(caproylamine), n-octylamine (caprylylamine), n-decylamine (caprylamine), n-
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dodecylamine (laurylamine), n-tetradecylamine (myristylamine), n-penta-
decylamine, n-hexadecylamine (palmitylamine), margarylamine, n-octadecyl-
amine (stearylamine)), unsaturated amines (such as dodecenylamine,
myristoleylamine, palmitoleylamine, oleylamine, and linoleylamine), or
etheramines (such as those identified as SURFAMTm P 14AB (branched C14),
SURFAMTm P 16A (linear C16), and SURFAMTm P 17AB (branched C17)). A
detailed description of methods for preparing suitable tartrimides (by
reacting
tartaric acid with a primary amine) is disclosed in US Patent 4,237,022.
[0072] US Patent Applications 2010-0197536 (corresponding to US
60/939949, filed May 24, 2007) and US 2010-0093573 (corresponding to
60/939952, filed May 24, 2007) disclose in more detail useful
hydroxycarboxylic acid compounds for the present invention.
[0073] Canadian Patent 1 183 125; US Patent Publication numbers
2006/0183647 and US-2006-0079413; US Patent Application number
60/867402; and British Patent 2 105 743 A, all disclose useful examples of
suitable tartaric acid derivatives.
[0074] The compound derived from the hydroxy-carboxylic acid may be
present at 0.05 wt % to 1.5 wt %, or 0.05 wt % to 1 wt %, or 0.05 wt % to 0.8
wt % of the lubricating composition.
Phosphorus Compounds
[0075] The phosphorus compound may be selected from the group
consisting of an amine salt of a phosphoric acid ester (typically an amine
salt of
a phosphoric acid hydrocarbon ester), a phosphite having at least one
hydrocarbyl group with 4 or more carbon atoms, a second phosphite having at
least one hydrocarbyl group with 4 or more carbon atoms, and mixtures thereof
[0076] In one embodiment the phosphorus compounds may be an amine salt
of a phosphoric acid ester (typically a phosphate of a hydrocarbon ester), and
a
phosphite, wherein the phosphite has at least one hydrocarbyl group with 4 or
more carbon atoms.
[0077] In one embodiment the phosphorus compounds may be an amine salt
of a phosphoric acid ester (typically a phosphate of a hydrocarbon ester), and
a
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phosphite, wherein the phosphite has at least one hydrocarbyl group with 4 or
more carbon atoms.
[0078] In one embodiment the phosphorus compounds are sulphur-free i.e.,
the phosphorus compound is not a thiophosphite, nor a thiophosphate.
[0079] The amount of phosphorus provided to the lubricating composition
by
the phosphorus compounds may, in certain embodiments, be 0.02 to 0.2 wt %, or
0.04 to 0.18 wt %, or 0.04 to 0.1 wt % or 0.08 to 0.18 wt % of the lubricating

composition.
Amine Salt of a Phosphoric Acid Ester
[0080] In one embodiment the lubricating composition contains a
phosphorus compound that may be an amine salt of a phosphoric acid ester
(typically an amine salt of a hydrocarbon ester of phosphoric acid). The amine

salt of the phosphate may be represented by the formula:
0 R5
R3-0õ..11 1 R6
+N/
P-0-
1 \
R4-0/ R7
R8
wherein
R3 and R4 may be independently hydrogen or a hydrocarbyl group (such as a
hydrocarbon group) typically containing 4 to 40, or 6 to 30, or 6 to 18, or 8
to
18 carbon atoms, with the proviso that at least one is a hydrocarbyl group;
and
R5, R6, R7 and R8 may be independently hydrogen or a hydrocarbyl group, with
the proviso that at least one is a hydrocarbyl group. Often the amine salt of
a
phosphoric acid ester may be a 1:1 mixture of di- and mono- alkyl, i.e., one
of
R3 or R4 may be hydrogen for half of the moles of the phosphoric acid ester.
[0081] The hydrocarbyl groups of R3 and/or R4 may be linear, branched, or
cyclic.
[0082] Examples of a hydrocarbyl group for R3 and/or R4 include straight-
chain or branched alkyl groups, including methyl, ethyl, propyl, butyl,
pentyl,

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hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,
pentadecyl, hexadecyl, heptadecyl and octadecyl.
[0083] Examples of a cyclic hydrocarbyl group for R3 and/or R4 include
cyclop entyl, cyclohexyl, cycloheptyl, methylcyclop entyl, dimethylcyclop
entyl,
methyl cyc lop entyl, dimethyl cyc lop entyl, methylethylcyclop entyl, diethyl-

cyclop entyl, methylcyclohexyl, dimethylcyclohexyl, methylethylcyclohexyl,
diethylcyclohexyl, methylcycloheptyl, dimethylcycloheptyl, methylethyl-
cycloheptyl, and diethylcycloheptyl.
[0084] In one embodiment the amine salt of a phosphoric acid ester is a
mixture of monoalkyl and dialkyl phosphoric acid esters. The monoalkyl and
dialkyl groups may be linear or branched.
[0085] The amine salt of a phosphoric acid ester (typically a hydrocarbon
ester) may be derived from an amine such as a primary amine, a secondary
amine, a tertiary amine, or mixtures thereof. The amine may be aliphatic, or
cyclic, aromatic or non-aromatic, typically aliphatic. In one embodiment the
amine includes an aliphatic amine such as a tertiary-aliphatic primary amine.
[0086] Examples of suitable primary amines include ethylamine,
propylamine,
butylamine, 2-ethylhexylamine, bis-(2-ethylhexyl)amine, octylamine, and
dodecyl-
amine, as well as such fatty amines as n-octylamine, n-decylamine, n-
dodecylamine, n-tetradecylamine, n-hexadecylamine, n-octadecylamine and
oleyamine. Other useful fatty amines include commercially available fatty
amines
such as "Armeen " amines (products available from Akzo Chemicals, Chicago,
Illinois), such as Armeen C, Armeen 0, Armeen OL, Armeen T, Armeen HT,
Armeen S and Armeen SD, wherein the letter designation relates to the fatty
group, such as coco, oleyl, tallow, or stearyl groups.
[0087] Examples of suitable secondary amines include dimethylamine,
diethylamine, dipropylamine, dibutylamine, diamylamine, dihexylamine,
diheptylamine, methylethylamine, ethylbutylamine, N-methyl-l-amino-cyclo-
hexane, Armeen 2C and ethylamylamine. The secondary amines may be
cyclic amines such as piperidine, piperazine and morpholine.
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[0088] Examples of tertiary amines include tri-n-butylamine, tri-n-
octylamine, tri-decylamine, tri-laurylamine, tri-hexadecylamine, and dimethyl-
oleylamine (Armeen0 DMOD).
[0089] In one embodiment the amines are in the form of a mixture.
Examples of suitable mixtures of amines include (i) a tertiary alkyl primary
amine with 11 to 14 carbon atoms, (ii) a tertiary alkyl primary amine with 14
to
18 carbon atoms, or (iii) a tertiary alkyl primary amine with 18 to 22 carbon
atoms. Other examples of tertiary alkyl primary amines include tert-
butylamine, tert-hexylamine, tert-octylamine (such as 1,1-dimethylhexylamine),

tert-decylamine (such as 1,1-dimethyloctylamine), tertdodecylamine, tert-
tetradecylamine, tert-hexadecylamine, tert-octadecylamine, tert-tetracosanyl-
amine, and tert-octacosanylamine.
[0090] In one embodiment a useful mixture of amines is "Primene0 81R" or
"Primene0 JMT." Primene0 81R and Primene0 JMT (both produced and sold
by Rohm & Haas) are mixtures of C11 to C14 tertiary alkyl primary amines and
C18 to C22 tertiary alkyl primary amines respectively.
[0091] The amine salt of a phosphoric acid ester may be prepared as
described in US Patent 6,468,946. Column 10, lines 15 to 63 describes
phosphoric acid esters formed by reaction of phosphorus compounds, followed
by reaction with an amine to form an amine salt of a phosphoric acid ester.
Column 10, line 64, to column 12, line 23, describes preparative examples of
reactions between phosphorus pentoxide with an alcohol (having 4 to 13 carbon
atoms), followed by a reaction with an amine (typically Primene081-R) to
form an amine salt of a phosphoric acid ester.
[0092] The amine salt of a phosphoric acid ester may be present at 0.1 wt
%
to 2.5 wt %, or 0.1 wt % to 1.5 wt %, or 1 wt % to 2 wt %, or 0.1 wt % to 1 wt
%
of the lubricating composition.
Phosphite
[0093] In one embodiment the lubricating composition contains a
phosphite,
wherein the phosphite has at least one hydrocarbyl group with 4 or more carbon

atoms. The phosphite hydrocarbyl group may have 8 or more, or 12 or more
carbon atoms. Typical ranges for the number of carbon atoms on the hydrocarbyl
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group include 4 to 30, or 10 to 24, or 12 to 22, or 14 to 20, or 16 to 18. The

phosphite may be a mono-hydrocarbyl substituted phosphite, a di-hydrocarbyl
substituted phosphite, or a tri-hydrocarbyl substituted phosphite.
[0094] The phosphite may be represented by the formulae:
R9
R9-0 H (::1
\ / Or
F'
k.... Rio
Rio_o
0 R i i c
wherein at least one or two of R9, R1 and R11 may be a hydrocarbyl group
containing at least 4 carbon atoms and the other may be hydrogen or a
hydrocarbyl group. In one embodiment two or more of R9, R1 and R11 are
hydrocarbyl groups. The hydrocarbyl groups may be alkyl, cycloalkyl, aryl,
acyclic or mixtures thereof. In the formula with all thee groups R9, R1 and
R11, the compound may be a tri-hydrocarbyl substituted phosphite i.e., R9, R1
and
R11 are all hydrocarbyl groups.
[0095] Alkyl groups may be linear or branched, typically linear, and
saturated or unsaturated, typically saturated. Examples of alkyl groups for
R9,
R1 and R11 include butyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl,
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
octadecenyl, nonodecyl, eicosyl or mixtures thereof.
[0096] Alkyl groups may be linear or branched, typically linear, and
saturated or unsaturated, typically saturated. Examples of alkyl groups for
R9,
R1 and R11 include butyl, hexyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl,
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,
octadecenyl, nonodecyl, eicosyl or mixtures thereof. In one embodiment the
alkyl groups R9 and R1 have 4 carbon atoms (typically n-butyl).
[0097] The amine salt of a phosphoric acid hydrocarbon ester and/or, a
phosphite having at least one hydrocarbyl group with 4 or more carbon atoms
may in one embodiment be in a mixture with one or more of phosphorus acid,
phosphoric acid, polyphosphoric acid, a trialkyl phosphate or trialkyl
thiophosphate. For instance the amine salt of a phosphoric acid hydrocarbon
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ester and/or, a phosphite having at least one hydrocarbyl group with 4 or more

carbon atoms may in one embodiment be in a mixture with phosphoric acid.
[0098] The phosphite compound may be present at 0.05 wt % to 2.0 wt %, or
0.05 wt % to 1.5 wt %, or 0.1 wt % to 1.0 wt % of the lubricating composition.

Oils of Lubricating Viscosity
[0099] The lubricating composition comprises an oil of lubricating
viscosity. Such oils include natural and synthetic oils, oil derived from
hydro cracking, hydrogenation, and hydrofinishing, unrefined, refined, re-
refined oils or mixtures thereof. A more detailed description of unrefined,
refined and re-refined oils is provided in International Publication
W02008/147704, paragraphs [0054] to [0056] (a similar disclosure is provided
in
US Patent Application 2010/197536, see [0072] to [0073]). A more detailed
description of natural and synthetic lubricating oils is described in
paragraphs
[0058] to [0059] respectively of W02008/147704 (a similar disclosure is
provided
in US Patent Application 2010/197536, see [0075] to [0076]). Synthetic oils
may also be produced by Fischer-Tropsch reactions and typically may be
hydroisomerised Fischer-Tropsch hydrocarbons or waxes. In one embodiment
oils may be prepared by a Fischer-Tropsch gas-to-liquid synthetic procedure as

well as other gas-to-liquid oils.
[0100] Oils of lubricating viscosity may also be defined as specified in
April 2008 version of "Appendix E - API Base Oil Interchangeability
Guidelines for Passenger Car Motor Oils and Diesel Engine Oils", section 1.3
Sub-heading 1.3. "Base Stock Categories". The API Guidelines are also
summarised in US Patent US 7,285,516 (see column 11, line 64 to column 12,
line 10). In one embodiment the oil of lubricating viscosity may be an API
Group II, Group III, Group IV oil, or mixtures thereof.
[0101] The amount of the oil of lubricating viscosity present is
typically the
balance remaining after subtracting from 100 wt % the sum of the amount of
the compound of the invention and the other performance additives.
[0102] The lubricating composition may be in the form of a concentrate
and/or a fully formulated lubricant. If the lubricating composition of the
invention (comprising the additives disclosed herein) is in the form of a
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concentrate which may be combined with additional oil to form, in whole or in
part, a finished lubricant), the ratio of the of these additives to the oil of

lubricating viscosity and/or to diluent oil include the ranges of 1:99 to 99:1
by
weight, or 80:20 to 10:90 by weight.
Organo-Sulphide
[0103] In one
embodiment the lubricating composition further comprises an
organo-sulphide, or mixtures thereof. In one embodiment the organo-sulphide
comprises at least one of a polysulphide, thiadiazole compound, or mixtures
thereof
[0104] In
different embodiments, the organo-sulphide is present in a range
selected from the group consisting of 0 wt % to 10 wt %, 0.01 wt % to 10 wt %,

0.1 wt % to 8 wt %, and 0.25 wt % to 6 wt %; of the lubricating composition.
Thiadiazole Compound
[0105]
Examples of a thiadiazole include 2,5-dimercapto-1,3,4-thiadiazole,
or oligomers thereof, a hydrocarbyl-substituted 2,5-dimercapto-1,3,4-
thiadiazole, a hydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazole,
or
oligomers thereof The oligomers of hydrocarbyl-substituted 2,5-dimercapto-
1,3,4-thiadiazole typically form by forming a sulphur-sulphur bond between
2,5-dimercapto-1,3,4-thiadiazole units to form oligomers of two or more of
said
thiadiazole units. These thiadiazole compounds may also be used in the post
treatment of dispersants as mentioned below in the formation of a
dimercaptothiadiazole derivative of a polyisobutylene succinimide.
[0106]
Examples of a suitable thiadiazole compound include at least one of a
dimercaptothiadiazole, 2,5-dimercapto-[1,3,4]-thiadiazole, 3,5-dimercapto-
[1,2,4]-thiadiazole, 3,4-dimercapto-[1,2,5]-thiadiazole, or 4-5-dimercapto-
[1,2,3]-
thiadiazole.
Typically readily available materials such as 2,5-di-
mercapto-1,3,4-thiadiazole or a hydrocarbyl-substituted 2,5-dimercapto-1,3,4-
thiadiazole or a hydrocarbylthio-substituted 2,5-dimercapto-1,3,4-thiadiazole
are
commonly utilised. In different embodiments the number of carbon atoms on the
hydrocarbyl-substituent group includes 1 to 30, 2 to 25, 4 to 20, 6 to 16, or
8 to 10.
[0107] In one
embodiment, the thiadiazole compound is the reaction product
of a phenol with an aldehyde and a dimercaptothiadiazole. The phenol includes

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an alkyl phenol wherein the alkyl group contains at least 6, e.g., 6 to 24, or
6 (or
7) to 12 carbon atoms. The aldehyde includes an aldehyde containing 1 to 7
carbon atoms or an aldehyde synthon, such as formaldehyde. Useful thiadiazole
compounds include 2-alkyldithio-5 -mercapto- [1,3,4] -thiadiazoles, 2,5 -
bis -
(alkyldithio)-[1 ,3 ,4] -thiadiazoles, 2 -alkylhydroxyphenylmethylthio -5 -
mercapto -
[1,3,4]-thiadiazoles (such as 245-hepty1-2-hydroxyphenylmethylthio]-5-
mercapto-[1,3,4]-thiadiazole), and mixtures thereof.
[0108] In one
embodiment the thiadiazole compound includes at least one of
2,5 -bis(tert-octyldithio)-1,3 ,4-thiadiazole, 2,5 -bis(tert-nonyldithio)-1,3
,4-thia-
diazole, or 2,5-bis(tert-decyldithio)-1,3,4-thiadiazole.
Polysulphide
[0109] In one
embodiment at least 50 wt % of the polysulphide molecules
are a mixture of tri- or tetra- sulphides. In other embodiments at least 55 wt
%,
or at least 60 wt % of the polysulphide molecules are a mixture of tri- or
tetra-
sulphides.
[0110] The
polysulphide includes a sulphurised organic polysulphide from oils,
fatty acids or ester, olefins or polyolefins.
[0111] Oils
which may be sulfurized include natural or synthetic oils such
as mineral oils, lard oil, carboxylate esters derived from aliphatic alcohols
and
fatty acids or aliphatic carboxylic acids (e.g., myristyl oleate and oleyl
oleate),
and synthetic unsaturated esters or glycerides.
[0112] Fatty
acids include those that contain 8 to 30, or 12 to 24 carbon
atoms. Examples of fatty acids include oleic, linoleic, linolenic, and tall
oil.
Sulphurised fatty acid esters prepared from mixed unsaturated fatty acid
esters
such as are obtained from animal fats and vegetable oils, including tall oil,
linseed oil, soybean oil, rapeseed oil, and fish oil.
[0113] The
polysulphide includes olefins derived from a wide range of
alkenes. The alkenes typically have one or more double bonds. The olefins in
one embodiment contain 3 to 30 carbon atoms. In other embodiments, olefins
contain 3 to 16, or 3 to 9 carbon atoms. In one embodiment the sulphurised
olefin includes an olefin derived from propylene, isobutylene, pentene or
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mixtures thereof Often the sulphurised olefin may be formed in the presence
of hydrogen sulphide (H2S).
[0114] In one embodiment the polysulphide comprises a polyolefin derived
from polymerising by known techniques, an olefin as described above.
[0115] In one embodiment the polysulphide includes dibutyl tetrasulphide,
sulphurised methyl ester of oleic acid, sulphurised alkylphenol, sulphurised
dipentene, sulphurised dicyclopentadiene, sulphurised terpene, and sulphurised

Diels-Alder adducts.
Friction Modifier
[0116] In one embodiment the lubricating composition further comprises a
friction modifier. In different embodiments, the friction modifier is present
in
a range selected from the group consisting of 0 wt % to 5 wt %, 0.1 wt % to 4
wt %, 0.25 wt % to 3.5 wt %, 0.5 wt % to 2.5 wt %, and 1 wt % to 2.5 wt %, or
0.05 wt % to 0.5 wt % of the lubricating composition.
[0117] As used herein the term "fatty alkyl" or "fatty" in relation to
friction
modifiers means a carbon chain having 10 to 22 carbon atoms, typically a
straight carbon chain.
[0118] The friction modifier includes fatty amines, borated glycerol
esters,
fatty acid amides, non-borated fatty epoxides, borated fatty epoxides,
alkoxylated fatty amines, borated alkoxylated fatty amines, metal salts of
fatty
acids, fatty imidazolines, metal salts of alkyl salicylates (may also be
referred
to as a detergent), metal salts of sulphonates (may also be referred to as a
detergent), condensation products of carboxylic acids or polyalkylene-
polyamines, or amides of hydroxyalkyl compounds.
[0119] In one embodiment the friction modifier includes a fatty acid
ester of
glycerol. The final product may be in the form of a metal salt, an amide, an
imidazoline, or mixtures thereof. The fatty acids may contain 6 to 24, or 8 to

18 carbon atoms. The fatty acids may branched or straight-chain, saturated or
unsaturated. Suitable acids include 2-ethylhexanoic, decanoic, oleic, stearic,

isostearic, palmitic, myristic, palmitoleic, linoleic, lauric, and linolenic
acids,
and the acids from the natural products tallow, palm oil, olive oil, peanut
oil,
corn oil, and Neat's foot oil. In one embodiment the fatty acid is oleic acid.
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When in the form of a metal salt, typically the metal includes zinc or
calcium;
and the products include overbased and non-overbased products. Examples are
overbased calcium salts and basic oleic acid-zinc salt complexes which can be
represented by the general formula Zn4Oleate60. When in the form of an
amide, the condensation product includes those prepared with ammonia, or with
primary or secondary amines such as diethylamine and diethanolamine. When
in the form of an imidazoline, the condensation product of an acid with a
diamine or polyamine such as a polyethylenepolyamine. In one embodiment
the friction modifier is the condensation product of a fatty acid with C8 to
C24
atoms, and a polyalkylene polyamine, and in particular, the product of
isostearic acid with tetraethylenepentamine.
[0120] In one embodiment the friction modifier includes those formed by
the condensation of the hydroxyalkyl compound with an acylating agent or an
amine. A more detailed description of the hydroxyalkyl compound is described
in WO 2007/0044820 paragraphs 9, and 20-22. The friction modifier disclosed
in W02007/044820 includes an amide represented by the formula
R12R13N_c(0)R145
wherein R12 and R13 are each independently hydrocarbyl
groups of at least 6 carbon atoms and R14 is a hydroxyalkyl group of 1 to 6
carbon atoms or a group formed by the condensation of said hydroxyalkyl
group, through a hydroxyl group thereof, with an acylating agent. Preparative
Examples are disclosed in Examples 1 and 2 (paragraphs 72 and 73 of
W02007/044820). In one embodiment the amide of a hydroxylalkyl compound
is prepared by reacting glycolic acid, that is, hydroxyacetic acid,
HO-CH2-COOH with an amine.
[0121] In one embodiment the friction modifier includes a secondary or
tertiary amine being represented by the formula R15R16NR175
wherein R15 and
R16 are each independently an alkyl group of at least 6 carbon atoms and R17
is
hydrogen, a hydrocarbyl group, a hydroxyl-containing alkyl group, or an
amine-containing alkyl group. A more detailed description of the friction
modifier is described in US Patent Application 2005/037897 in paragraphs 8
and 19 to 22.
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[0122] In one
embodiment the friction modifier includes a reaction product
of a di-cocoalkyl amine (or di-cocoamine) with glycolic acid. The friction
modifier includes compounds prepared in Preparative Examples 1 and 2 of WO
2008/014319.
[0123] In one
embodiment the friction modifier includes those derived from
the reaction product of a carboxylic acid or a reactive equivalent thereof
with
an aminoalcohol, wherein the friction modifier contains at least two
hydrocarbyl groups, each containing at least 6 carbon atoms. An example of
such a friction modifier includes the reaction product of isostearic acid or
an
alkyl succinic anhydride with tris-hydroxymethylaminomethane. A more
detailed description of such a friction modifier is disclosed in US Patent
Application 2003/22000 (or International Publication W004/007652) in
paragraphs 8 and 9 to 14.
[0124] In one
embodiment the friction modifier includes an alkoxylated
alcohol. A detailed description of suitable alkoxylated alcohols is described
in
paragraphs 19 and 20 of US Patent Application 2005/0101497. The
alkoxylated amines are also described in US Patent 5,641,732 in column 7, line

15 to column 9, line 25.
[0125] In one
embodiment the friction modifier includes a hydroxyl amine
compound as defined in column 37, line 19, to column 39, line 38 of US Patent
5,534,170. Optionally the hydroxyl amine includes borated as such products
are described in column 39, line 39 to column 40 line 8 of US Patent
5,534,170.
[0126] In one
embodiment the friction modifier includes an alkoxylated
amine e.g., an ethoxylated amine derived from 1.8 % EthomeenTM T-12 and
0.90 % TomahTm PA-1 as described in Example E of US Patent 5,703,023,
column 28, lines 30 to 46. Other suitable alkoxylated amine compounds
include commercial alkoxylated fatty amines known by the trademark
"ETHOMEEN" and available from Akzo Nobel. Representative examples of
these ETHOMEENTm materials is ETHOMEENTm C/12 (bis[2-hydroxyethy1]-
co co -amine); ETHOMEENTm C/20
(polyoxyethylene [10] cocoamine);
ETHOMEENTm S/12 (bis[2-hydroxyethyl]soyamine); ETHOMEENTm T/12
(bis[2-hydroxyethyl] -tallow-amine); ETHOMEENTm T/15 (polyoxyethylene-
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[5]tallowamine); ETHOMEENTm 0/12 (bis[2-hydroxyethyl]oleyl-amine);
ETHOMEENTm 18/12 (bis[2¨hydroxyethyl]octadecylamine); and
ETHOMEENTm 18/25 (polyoxyethylene[15]octadecylamine). Fatty amines and
ethoxylated fatty amines are also described in U.S. Patent 4,741,848.
[0127] In one
embodiment the friction modifier includes a polyol ester as
described in US Patent 5,750,476 column 8, line 40 to column 9, line 28.
[0128] In one
embodiment the friction modifier includes a low potency
friction modifier as described in US Patent 5,840,662 in column 2, line 28 to
column 3, line 26. US Patent 5,840,662 further discloses in column 3, line 48
to column 6, line 25 specific materials and methods of preparing the low
potency friction modifier.
[0129] In one
embodiment the friction modifier includes a reaction product
of an isomerised alkenyl substituted succinic anhydride and a polyamine as
described in US Patent 5,840,663 in column 2, lines 18 to 43. Specific
embodiments of the friction modifier described in US Patent 5,840,663 are
further disclosed in column 3, line 23 to column 4, line 35. Preparative
examples are further disclosed in column 4, line 45 to column 5, line 37 of US

Patent 5,840,663.
[0130] In one embodiment the friction modifier includes an
alkylphosphonate mono- or di- ester sold commercially by Rhodia under the
trademark Duraphos0 DMODP.
[0131] In one
embodiment the friction modifier includes a borated fatty
epoxide or alkylene oxide, known from Canadian Patent No. 1,188,704. These
oil-soluble boron-containing compositions are prepared by reacting, at a
temperature of 80 C to 250 C, boric acid or boron trioxide with at least one
fatty epoxide or alkylene oxide. The fatty epoxide or alkylene oxide typically

contains at least 8 carbon atoms in the fatty groups of the epoxide (or the
alkylene groups of the alkylene oxide).
[0132] The
borated fatty epoxides include those characterised by the method
for their preparation which involves the reaction of two materials. Reagent A
includes boron trioxide or any of the various forms of boric acid including
metaboric acid (HB02), orthoboric acid (H3B03) and tetraboric acid (H2B407),

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or orthoboric acid. Reagent B includes at least one fatty epoxide. The molar
ratio of reagent A to reagent B is generally 1:0.25 to 1:4, or 1:1 to 1:3, or
1:1 to
1:2. The borated fatty epoxides includes compounds prepared by blending the
two reagents and heating them at temperature of 80 C to 250 C, or 100 C to
200 C, for a period of time sufficient for reaction to take place. If
desired, the
reaction may be effected in the presence of a substantially inert, normally
liquid organic diluent. During the reaction, water is evolved and may be
removed by distillation.
Other Performance Additive
[0133] The composition of the invention optionally further includes at
least
one other performance additive. The other performance additives include metal
deactivators, dispersants (other than the non-borated dispersant of the
present
invention), viscosity modifiers, dispersant viscosity modifiers, antioxidants,

corrosion inhibitors, foam inhibitors, demulsifiers, pour point depressants,
seal
swelling agents, phosphoric acid, and mixtures thereof.
[0134] In different embodiments, the total combined amount of the other
performance additive compounds is present in a range selected from the group
consisting of 0 wt % to 75 wt %, 0.1 wt % to 50 wt %, and 0.5 wt % to 30 wt
%, 0.5 wt % to 15 wt % or to 10 wt %, of the lubricating composition.
Although one or more of the other performance additives may be present, it is
common for the other performance additives to be present in different amounts
relative to each other.
[0135] Antioxidants include molybdenum compounds such as molybdenum
dithiocarbamates, sulphurised olefins, hindered phenols, aminic compounds
such as phenyl-a-naphthylamine (PANA) or alkylated diphenylamines (typically
di-nonyl diphenylamine, octyl diphenylamine, or di-octyl diphenylamine).
[0136] Viscosity modifiers include hydrogenated copolymers of styrene-
butadiene, ethylene-propylene copolymers, polyisobutenes, hydrogenated
styrene-isoprene polymers, hydrogenated isoprene polymers, polymethacrylate
acid esters, polyacrylate acid esters, polyalkyl styrenes, alkenyl aryl
conjugated
diene copolymers, polyolefins, polyalkylmethacrylates and esters of maleic
anhydride-styrene copolymers. Dispersant viscosity modifiers (often referred
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to as DVM) include functionalised polyolefins, for example, ethylene-
propylene copolymers that have been functionalized with the reaction product
of maleic anhydride and an amine, a polymethacrylate functionalised with an
amine, or styrene-maleic anhydride copolymers reacted with an amine; may
also be used in the composition of the invention.
[0137] Corrosion inhibitors include 1-amino-2-propanol, amines, triazole
derivatives including tolyl triazole, dimercaptothiadiazole derivatives,
octylamine octanoate, condensation products of dodecenyl succinic acid or
anhydride and/or a fatty acid such as oleic acid with a polyamine.
[0138] Foam inhibitors that may be useful in the compositions of the
invention include polysiloxanes, copolymers of ethyl acrylate and 2-
ethylhexylacrylate and optionally vinyl acetate; demulsiflers including
fluorinated
polysiloxanes, trialkyl phosphates, polyethylene glycols, polyethylene oxides,

polypropylene oxides and (ethylene oxide-propylene oxide) polymers.
[0139] Pour point depressants that may be useful in the compositions of
the
invention include polyalphaolefins, esters of maleic anhydride-styrene
copolymers, poly(meth)acrylates, polyacrylates or polyacrylamides.
[0140] Demulsifiers include trialkyl phosphates, and various polymers and
copolymers of ethylene glycol, ethylene oxide, propylene oxide, or mixtures
thereof
[0141] Metal deactivators include derivatives of benzotriazoles
(typically
tolyltriazole), 1,2,4-triazoles, benzimidazoles, 2-alkyldithiobenzimidazoles
or
2-alkyldithiobenzothiazoles. The metal deactivators may also be described as
corrosion inhibitors.
[0142] Seal swell agents include sulfolene derivatives, Exxon Necton37TM
(FN 1380) and Exxon Mineral Seal Oi1TM (FN 3200).
[0143] In different embodiments the lubricating composition of the
invention may or may not contain phosphoric acid.
Industrial Application
[0144] The method of the invention is useful for lubricating a variety of
driveline devices applications. The driveline device comprises at least one of
a
gear, a gearbox, an axle gear, a traction drive transmission, an automatic
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transmission or a manual transmission. In one embodiment the driveline device
is a manual transmission or a gear, a gearbox, or an axle gear.
[0145] An automatic transmission includes continuously variable
transmissions (CVT), infinitely variable transmissions (IVT), toroidal trans-
missions, continuously slipping torque converter clutches (CSTCC), stepped
automatic transmissions or dual clutch transmissions (DCT).
[0146] Automatic transmissions can contain continuously slipping torque
converter clutches (CSTCC), wet start and shifting clutches and in some cases
may also include metal or composite synchronizers.
[0147] Dual clutch transmissions or automatic transmissions may also
incorporate electric motor units to provide a hybrid drive.
[0148] A manual transmission lubricant may be used in a manual gearbox
which may be unsynchronized or may contain a synchronizer mechanism. The
gearbox may be self-contained or may additionally contain any of a transfer
gearbox, planetary gear system, differential, limited slip differential or
torque
vectoring device, which may be lubricated by a manual transmission fluid.
[0149] The gear oil or axle oil may be used in a planetary hub reduction
axle, a mechanical steering and transfer gear box in utility vehicles, a
synchromesh gear box, a power take-off gear, a limited slip axle, and a
planetary hub reduction gear box.
[0150] Unless otherwise indicated, each chemical or composition referred
to
herein should be interpreted as being a commercial grade material which may
contain the isomers, by-products, derivatives, and other such materials which
are normally understood to be present in the commercial grade. However, the
amount of each chemical component is presented exclusive of any solvent or
diluent oil, which may be customarily present in the commercial material,
unless otherwise indicated.
[0151] The following examples provide illustrations of the invention.
These
examples are non-exhaustive and are not intended to limit the scope of the
invention.
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EXAMPLES
[0152] A series of gear oil lubricants are prepared containing an amount
of
each of the following: (a) an amine salt of a phosphoric acid, (b) a
phosphite,
(c) a derivative of a hydroxy-carboxylic acid, (d) a polyisobutylene
succinimide
(non-borated), (e) a detergent, and 36.5 wt % actives of a viscosity modifier.

The lubricants contain amounts shown in the following table:
Amounts Quoted on wt % basis
Example (a) (b) (c) (d) (e)
EX1 1.4 0.20 0.10 2.00 0.55
EX2 1.4 0.35 0.10 2.00 1.37
EX3 1.4 0.50 0.10 2.00 1.37
EX4 1.0 0.50 0.25 2.00 1.37
EX5 1.3 0.50 0.20 1.30 0.78
EX6 1.1 0.50 0.25 2.00 1.37
EX7 1.3 0.90 0.30 1.50 0.98
EX8 1.7 0.90 0.50 0.00 1.37
EX9 1.0 0.86 0.10 1.95 1.37
EX10 1.8 0.46 0.10 1.25 1.37
EX11 1.0 0.50 0.05 1.50 0.50
EX12 1.5 0.30 0.20 1.50 0.50
EX13 1.4 0.10 0.25 1.50 0.75
EX14 1.3 0.50 0.10 2.00 0.75
EX15 1.5 0.70 0.20 1.20 1.42
EX16 1.1 0.85 0.30 2.00 0.50
EX17 2.0 0.90 0.10 1.50 0.25
EX18 1.0 0.86 0.20 1.95 0.75
EX19 1.0 0.50 0.20 1.95 0.30
Footnote:
Amounts quoted for (d) include 14-50 wt % of diluent oil.
Examples 1-10 are SAE grade 75W-90 fluids containing a magnesium
detergent, and the quantity shown includes 39 wt % of diluent oil.
29

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Example 11-18 are SAE grade 75W-90 fluids containing a calcium detergent
and the quantity shown includes 42 wt % of diluent oil.
[0153] A series of gear oil lubricants are prepared containing an amount
of
each of the following: (a) an amine salt of a phosphoric acid, (b) a
phosphite,
(c) a derivative of a hydroxy-carboxylic acid, (d) a polyisobutylene
succinimide
(non-borated), (e) a detergent, and 5 wt % actives of a viscosity modifier.
The
lubricants contain amounts shown in the following table:
Amounts Quoted on wt % basis
Example (a) (b) (c) (d) (e)
EX20 0.50 0.30 0.05 0.05 0.25
EX21 0.10 0.10 0.10 0.20 0.25
EX22 0.37 0.18 0.10 0.75 0.8
EX23 0.37 0.18 0.10 0.75 0.625
EX24 0.60 0.30 0.10 0.10 0.75
EX25 0.60 0.10 0.15 0.10 0.75
EX26 0.20 0.30 0.10 0.10 0.75
EX27 0.50 0.10 0.15 0.10 0.75
Footnote:-
Amounts quoted for (d) include 14-50 wt % of diluent oil.
Examples 20-27 are SAE grade 75W-80 fluids containing a calcium detergent,
and the quantity shown includes 42 wt % of diluent oil.
[0154] Overall, the compositions of the invention have performance
benefits
over comparative examples in least one of (i) wear, (ii) scuffing, (iii)
fatigue, (iv)
ridging, (v) extreme pressure performance, (vi) fuel economy/efficiency
(typically
improving fuel economy/efficiency), (vii) oxidation control (typically
reducing or
preventing oxidation), (viii) friction performance and (ix) deposit control.
[0155] It is known that some of the materials described above may
interact
in the final formulation, so that the components of the final formulation may
be
different from those that are initially added. The products formed thereby,
including the products formed upon employing lubricant composition of the
present invention in its intended use, may not be susceptible of easy
description. Nevertheless, all such modifications and reaction products are

CA 02827472 2013-08-15
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included within the scope of the present invention; the present invention
encompasses lubricant composition prepared by admixing the components
described above.
[0156] Each of the documents referred to above is incorporated herein by
reference. Except in the Examples, or where otherwise explicitly indicated,
all
numerical quantities in this description specifying amounts of materials,
reaction
conditions, molecular weights, number of carbon atoms, and the like, are to be

understood as modified by the word "about." It is to be understood that the
upper
and lower amount, range, and ratio limits set forth herein may be
independently
combined. Similarly, the ranges and amounts for each element of the invention
may be used together with ranges or amounts for any of the other elements.
[0157] As used herein, the term "hydrocarbyl substituent" or "hydrocarbyl
group" is used in its ordinary sense, which is well-known to those skilled in
the
art. Specifically, it refers to a group having a carbon atom directly attached
to
the remainder of the molecule and having predominantly hydrocarbon
character. Examples of hydrocarbyl groups include: hydrocarbon substituents,
including aliphatic, alicyclic, and aromatic substituents; substituted
hydrocarbon substituents, that is, substituents containing non-hydrocarbon
groups which, in the context of this invention, do not alter the predominantly

hydrocarbon nature of the substituent; and hetero substituents, that is,
substituents which similarly have a predominantly hydrocarbon character but
contain other than carbon in a ring or chain. A more detailed definition of
the
term "hydrocarbyl substituent" or "hydrocarbyl group" is described in
paragraphs [0118] to [0119] of International Publication W02008147704.
[0158] As used herein the term "fatty" as in fatty acid (and other
expressions used herein) includes a hydrocarbyl chain containing 4 to 150, or
4
to 30, or 6 to 16 carbon atoms.
[0159] While the invention has been explained in relation to its
preferred
embodiments, it is to be understood that various modifications thereof will
become apparent to those skilled in the art upon reading the specification.
Therefore, it is to be understood that the invention disclosed herein is
intended
to cover such modifications as fall within the scope of the appended claims.
31

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Administrative Status

Title Date
Forecasted Issue Date 2019-08-20
(86) PCT Filing Date 2012-02-15
(87) PCT Publication Date 2012-08-23
(85) National Entry 2013-08-15
Examination Requested 2017-02-15
(45) Issued 2019-08-20

Abandonment History

There is no abandonment history.

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Payment History

Fee Type Anniversary Year Due Date Amount Paid Paid Date
Registration of a document - section 124 $100.00 2013-08-15
Application Fee $400.00 2013-08-15
Maintenance Fee - Application - New Act 2 2014-02-17 $100.00 2014-01-21
Maintenance Fee - Application - New Act 3 2015-02-16 $100.00 2015-01-20
Maintenance Fee - Application - New Act 4 2016-02-15 $100.00 2016-01-22
Maintenance Fee - Application - New Act 5 2017-02-15 $200.00 2017-01-19
Request for Examination $800.00 2017-02-15
Maintenance Fee - Application - New Act 6 2018-02-15 $200.00 2018-01-19
Maintenance Fee - Application - New Act 7 2019-02-15 $200.00 2019-01-21
Final Fee $300.00 2019-06-21
Maintenance Fee - Patent - New Act 8 2020-02-17 $200.00 2020-02-07
Maintenance Fee - Patent - New Act 9 2021-02-15 $204.00 2021-02-05
Maintenance Fee - Patent - New Act 10 2022-02-15 $254.49 2022-02-11
Maintenance Fee - Patent - New Act 11 2023-02-15 $263.14 2023-02-10
Maintenance Fee - Patent - New Act 12 2024-02-15 $347.00 2024-02-09
Owners on Record

Note: Records showing the ownership history in alphabetical order.

Current Owners on Record
THE LUBRIZOL CORPORATION
Past Owners on Record
None
Past Owners that do not appear in the "Owners on Record" listing will appear in other documentation within the application.
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Document
Description 
Date
(yyyy-mm-dd) 
Number of pages   Size of Image (KB) 
Abstract 2013-08-15 1 54
Claims 2013-08-15 4 193
Description 2013-08-15 31 1,520
Cover Page 2013-10-21 1 31
Claims 2017-02-15 3 112
Examiner Requisition 2018-02-12 3 174
Amendment 2018-08-13 11 297
Claims 2018-08-13 4 113
Final Fee 2019-06-21 1 49
Cover Page 2019-07-22 1 30
PCT 2013-08-15 22 1,031
Assignment 2013-08-15 11 386
Amendment 2017-02-15 4 155